Stabilization of coloring compositions containing diazonium salts



Patented'Oct. 9, 1945' Frederic B. Adams, Bound Brook, Hans Z. Lccher,Plainlield, and William B. Hardy, Bound Brook, N. J assignors toAmerican Cyanamid Com-' pany, New York, N. Y., a corporation of Maine NoDrawing. Application July 5, 1943, a 1 6 Serial NQ.'Q93,592

, This invention relates to compositions contain-- ing diazonium saltsderived from ice color diazo components and to methods of preventing thethinning of printing pastes containing such diazo compounds.

An important method of producing prints of azoic colors on vegetablefibers consists in padding the goods with an alkaline solution of anazoic coupling component and printing these goods with a printing pastecontaining a diam-- nium salt derived from an ice color diazo coni-Claims. '(01. 8-44)] double bonds,-borofluorides, particularly salts of.complexacids sometimes referred to as double -salts, the most importantof them being the double ponent. The diazonium salt is either preparedby the printer, himself by diazotijzing the corresponding base orit isapplied in the form-of a stable diazonium salt. This'simple andwellknown cheap process is open to a very seriousdisadvantage.

- the diazonium salts and a carbohydrate thickener The printing pastescontaining tend to thin out rapidly losing their desired printingconsistency. It is with this thinning action that the present inventionis concerned.

According to the present invention the diazoenous base soluble inaqueous mineral acids and containing at least one olefinic double bondor one acetylenic triple bond for each 12 carbon atoms. When an aromaticamine is diazotized in acid solution, a diazonium salt is formed whichis generally assumed to have the following formula:

Others are not so soluble and can be easily isolated. Some are difiicultto handle after isolation because oftheir explosiveness, others arerather stable and do not present an explosive hazard.

' It is also known that if the anion of the acid X- is properly chosen,in almost all cases diazonium salts of lower solubility may be producedand thereforeisolated, audit is also known thatmany of these diazoniumsalts have lost their explosive character and can be stored and handledin the dry state without danger; this kind of diazonium salts issometimes referred to as stabilized diazonium salts. They comprise suchcompounds as certain aromatic sultonates, without olefliiic l v I mmsalt is associated with an organic nitrogsaltsof diazonium chlorides andzinc which correspond to the iormula:

(4 11)" (zno1.)= 1 1 l K I It should be borne in mind that also thesestachloride bilized diazoniuin salts including the above mentioneddouble salts are true 'azonium salts, i. e. the aqueous solutioncontains the same diazonium cations asthe solution of any otherdiazonium salt derived from the same base.

The stabilized diazonium salts should not be confused with other kindsof stabilized diazo compounds such as diazota'tes, also known asnitrosamines, or diazo amino and diazo imino coma pounds which are only}stable and applied in 611- kaline medium, while on the other hand thediazonium salts are only stable and applied in acid medium. The presentinvention deals with inhibiting the thinning action of diazonium saltsonly and not with any similar actionthat might be observed with othertypes of diazo compounds. Whenever stabilized diazo compounds arereferred to in this application this term shall be interpreted toinclude exclusively stabilized diazonium salts and not to includediazotates or diazo amino or diazo imino compounds.

While it is not intended to limit the present invention to any theory ofaction, we believe that nitrosamines.

it is highly probable that lowering of viscosity of printing gums isessentially caused by the diazonium cation because the same kind ofthing results regardless of the anion of the diazonium salt and even thedouble salts of the stabilized diazoniumsalts described above exert asimilar thinning action. Presumably in aqueous solution the stabilizeddiazonium salts are ionized to give the same diazonium cation. The pH ofthe printing paste'is not critical so long as it is on the acid side forthe present invention does not deal with any other types of pastes.\Alkaline media, as is well known, cause rearrangement of the diazoniumsalts to diazo compounds of different structure which are referred to asdiazotates or While not desiring to to, we believe that the evidencestrongly indicates that the thinning action is a colloidal phenomenonrather than a chemical reaction.- The fol-.

lowing test was made:

oxy aniline was addedto a, printing paste made limit the inventionthere- .up with a starch thickener; after hours the then water thinsolution was coupled with an alkaline solution of beta-naphthol and theazo dye formed was removed by filtration. The amount.

very active couplers are also the worst thinners,

while those that are slow in coupling generally thin to a much lesserdegree. Though there is certainly some parallelism in the coupling powerand thinning action these two properties are not strictly proportionate.The diazonium salts that derive from nitroanilines are the worstthinners. Particularly those deriving from 2,4-dinitro-6- chloroaniline,from -2-nitro-4-chioroaniline, from 2-nitro-i-methoxy aniline, from2-nitro-4- methylaniline thin the vegetable gums very badly. Thediazoniuni salts. deriving from o-nitraniline thin more than thosederiving from the meta and para compounds. On the other hand thediazonium salts deriving from the 2-methyl-4- chloroaniline and fromo-anisidine have only little thinning action. Qbviouslmthe rate of thethinning depends upon the concentration of the diasonium ions present inthe printing paste.

The thinning action has heenobserved with all thiclreners prepared frommaterials of vegetable origin such as starches, gums, alkyl celluloses,etc. Wheat starch, corn starch, rice starch, sweet potato starch,tapioca starch and chlorinated.

starch may be mentioned as esples of starches. Carob bean gum and gumtr-agacanth may be mentioned as examples of game, and methylorethyl-cellulose as examples of alkyl celluloses.

Obviously, also mixture of these materials are quite often used inthiclseners and their viscosity is equally iniiuencedhy diasoniunisalts. It will he noted that all of these thiclteners are carbohydratesor carbohydrate derivatives. In the claims the expression carbohydratethickener is used in a broad sense to cover pure carbohydrates andderivatives.

We have found that organic nitrogenous bases that are soluble in aqueousmineral acids and that contain at least one clefinic double bond or oneacetylenic triple bond for each 12 carbon atoms or their water solublesalts delay the thinning to such an extent thatit becomes harmless fromthe practical point of view.

We believe that the diazonium cations which are the active thinningagents are unsaturated and have a marked tendency to combine. Thisunsatmaterl character i probably responsible for the ease with whichthey combine with coupling components to form one dyestufis. When anunsaturated thinning inhiliitor such as an unsaturated nitrogenous baseis added to the diazoniurn salt solution before the printing thickeneris added, it is probable that the diaaonlum cation forms a loose complexwith the thinning inhibitor which decreases the aflinity of thediazonium c ation and inhibits its action upon the thickener. When thethickener is first added to the diazcnium salt solution followed byaddition of the thinning inhibitor, thinning is prevented to a muchlesser degree. Apparently in such a case the diazonium salt has alreadycommenced its thinning action on the thickener and the actitm aseaeacaromatic amines free from solubilizing groups useful in making icecolors or azoic pigments Typical are the following:

Aniline and its homologues, as e.- g. the toluidines,2,4-dimethy1aniline; halogen derivatives of aniline and of itshomologues, as e. g. the mono-fluoroanilines; the monochloranilines,2,5- difluoroaniline, 2 fluoro-E-chloroaniline, 2,5-dichloroaniline,m-aminobenzotrifiuoride, p-amino-benzotrifiuoride, Zi-amino 4chlorobenzotrifluoride, 2-methy1-3-chloroaniline, 2-methy1-4-chloroaniline, 2-methyl-5-chloroaniline, 3-methyl-4-chloroaniline,5-methyl-2-chloroaniline, 2- methyl 4-chloro 5-bromoaniline, 2methyl-4,5- dichloroanlline, 4 methyl 2,5 dichloroaniline; nitroderivatives of aniline and of its homologues and their halogenderivatives, as e. g. the nitroanilines, 2 -methyl-l-nitroaniline,2-methyl-5- nitroaniline, i-methyl-Z-nitroaniline, 2-nitr0-4-fiuoroaniiine, 2-nitro-4-chloroaniline, B-nitro-lchloroaniline,4-nitro-2-chloroaniline; ether derivatives of primary aromatic aminesand their halogen derivatives, as e. g. o-anisldine, Z-methoxy-S-methylaniline, 2,5 dimethoxy-aniline, 2-

- methoxy 1 naphthylamine, 2-aniino-diphenyino-Z-chloro-diphenylether, eamino-4'-chl0rocliphenyl ether, 4,4 dichlcr-Q-amino-diphenylii ether,2,2, trichloro i-arnino-diphenylether;

ether derivatives of aniline and its homologues containing nitro groupsas e. g. 2-methoxy-4-nitroaniline, 2-n1ethoxy-5-riitroaniline,Z-nitro-imethoxyaniline, Z-methoxy-d-nitro 5 methylaniline; monoacylderivatives of aromatic diarnines; as e. g,N-hexahydrobemoyl-p-phenylene diamine, N- hexahydrobenzoyl-p-toluylenediamine, N-benzoybp-phenylene diainine; monoacyl derivatives ordiamino-phenol ethers as e. g. 2 henzoylainino-l-aminoanisole, 2hexahydrobenzoylamino 5 aminoanisole,2-arnino-5-benzoylamine-hydroquinone dimethylether and di--' ethylether,2 amino-5-hexahydrobenzoyleminohydroquinone dimethylether anddiethylether, 2-amino-5-butyrylamino hydroquinone dimethylether anddiethylether, Z-amino-E-phenoxyacetylarnino-hydroquinone diethylether,the monomethyl and the monobenzyl and the monophonyl-urethane of2,5-diamino-hydroquinone dimethylether and diethylether,1-amino-3-benzoyla nino 4,6 dimethoxy-benzene; analogous monoacylderivatives of 2,5-diaminoi-allroxytoluenes and of2,5-diamino-4-alkoxy-chlorcbentones and of 2,5-diamino-i-alkoXy-benzenesulfodialkylamides; analogous monoacyl derivatives of1,3-diamino-i,5-dimethylbenzene; the diethylamide of2-amino-i(i'-chlorophenory)-benzoic acid; monoacyl derivatives ofdiamino-p-chlorophenyl others as e. g.2-amino-4-chloro-5-acetylaminodiphenylether,2-benzoylaminoi-chlorofi-aminoanisole amino derivatives of aromaticsulfones as e. g. 3-amino-4-rnethyl-diphenyl sulione,2-amino-4'-methyl-diphenyl sulfone, 2- amino-4-acetyl-diphenylsulfone,'the ethyl ester of 3-amino-4- (p-toluene-sulfony1) -benz'oicacid,

7 v 2,aso,c4'e I '3 4-methoxy 3 amino phenyl-ethylsulfone, (4'- metho'xy3 amino-phenyl) -benzyl' 'sulfone, 4-

ethoxy 3 amino-diphenyl' sulfone. 2-amino-4-v (trifluoromethyll-phe'nylethyl sulfone;' amino derivatives of aromatic" dialkylsulfonamides as e.g. 3-amino-4-methyl benzenedimethylsulfonamide and diethylsulfonamide, 3amino-4-methoxy-benzene diethylsulfonamidef xenylamine;

- alpha. and beta naphthylamine; ,alpha amino anthraquinone; 2amino-3-nitro-fluorene and 2.-

amino-3-nitro-fluorenone; amino diarylamines and their ether derivativesand their nitro. de-

' rivatives as e. g. 2-methoxy-5-aminodiphenylamine, 4methoxyi'-amino-diphenylamine, 4-

ethoxy-4'-amino-diphenylamine, 3,4 dimtI'O-4- amino-diphenylamine;amino-azo compounds, as e. 'g. 3,2'-dimethyl-4-amino-azobenzene,Z-methyl 4 amino-5-methoxy-4-chloroazobenzene, 4-

. amino-4'-nitro 3-methoxy-6#methyl-azobenzene,

' onto alpha naphthylamine.

4 amino-4'-nitro-2,5 dimethoxy-azobenzene, 4-amino-4-chloro-3-methoxy-61- methyl azobenzene, the azo dye: diazotizedo-anisidine coupled There are also diazonium salts deriving fromaromatic diamines in which only ,one of the amino groups is diazotizedand they also fall within the scope of the presentinvention. An exampleof this type of amine is 2,6-dichlro'-l,4-phenylene diamine. "Diazoniumsalts deriving from diamines in which both amino groups are'diazo tizedto form tetrazo compounds fall within its scope. Typical amines of thisclass are p-phen- Y ylene diamine, benzidine, o-tolidine, o-dianisidine,4,4'-diamino stilbene, 4,4'-diamino diphenj yl-amine, 2,2dimethyl-4,4'-diamino diphenylamine and 1,5-diamino naphthalene.

, also diazonium salts deriving from heterocyclic amines or diaminesfall under the present invention. Typical heterocyclic amines'are2-aminocarbazole, 3,6 diaminocarbazole, 2 nitro 3 [Obviously alsomixtures of different diazonium. salts may be used.

The inhibitors claimed in the present invention salts regardless of theform in which they are in- 'troduced. It is also necessary that thebases and their salts be .free from constituents capable-of bonds oracetylenic triple bonds.

- azoic coupling with the diazonium salt, condensation therewith to formdiazoamino or diazoimino compounds in acid medium, or'catalytic decom'-'position thereof at room temperatures. The sec- .ond limitation is not'a serious one as it isdiflicult to form a diazoamino or diazoiminocompound under the acid conditions which obtainin the compositions ofthe present invention. Examples of compounds whichcatalyticallydecompose the diazonium salts are iodides of the inhibiting bases. I ormore basic nitrogenous groups and, of course, they may contain one ormore olefinic double The same molecule may also contain both kinds ofbonds. Theportion ofthe molecule containing the unsaturated bonds may beconnected to the basic nitrogenous groups through a carbon chain or acarbon chain interrupted by other elements such as oxygen, nitrogen,sulfur, and the like. The invention is not limited tothe use of anysingle inhibitor and mixtures may be employed where desired.

The organic nitrogenous bases may be divided into two main groups- Inthe first group the basic portion of the molecule contains only onenitrogen atom connected with the same carbon atom and this groupcomprises the primary, secondary and tertiary amines and the quaternarybases. It also comprises compounds which contain two or more such groupswhich, however, are not connected f with the same carbon atom. Inthesecond group the basic part of the molecule contains two or threenitrogen atoms connected with the same carbon, atom and this groupcomprises amidines and the closely related isoureas, isothioureas,

guanidines, ureas, etc.

. tene-l, 5-amino-hexene-l, 4-allyl-5-amino pencomprise' all organicnitrogenous basesthat are- I soluble in aqueous mineral acids and thatcontain at least one olefinic double bond or at least one .acetylenictriple bond. .We have found that the olefinic double bond or acetylenictriple bond appears to. be mainly responsible for the anti-thinningaction of the nitrogenous bases'of the. present invention. However, wehave found that there there is at least one olefinic double bond oracetylenic triple bond for each 12 carbon atoms of the nitrogenous base.In addition to the above limitation on the nitrogenous base. it isnecessary that the base be soluble inmineral acids since the printingpastes containing the diazonium salts are always acid. The bases may beused as such if there is sufiicient acid in the printing paste to bothneutralize and dissolve them, or they may be-used in the form of any oftheir water soluble salts.

.doubtedly exist in the form of their water soluble In factin theprinting paste they untetra-allylethylene diamine.

tene-l, 2,6 dimethyl 8 amino .0ctadiene-2,6,

(beta-amino ethyD-allyl ether and thioether,

N,N,Nf,N'-

2-propynylamine (proparglyamine),

As examples of aliphatic bases belonging to the second group there maybe mentioned N-allylurea. N-ethyl N allylurea, N,N'-diallylurea, O-allylisourea, S-allyl isothiourea, S-beta-methyl-allyl isothiourea, allylguanidine, omega-allyl-biguanide.

It is not necessary that the bases of the present invention belong tothe aliphatic series. and bases having ring systems are also included,provided they contain at least one double bond of olefinic character orat least one triple bond. It should be noted that double bonds occurringin aromatic r ngs are-not of olefinic nature. Thus N-phenyl-N,N,N-trimethyl ammonium hydroxide is not an inhibitor covered by thepresent invention because the benzene ring does not contain olefinicdouble bonds. However, unsaturated alicyclic bases are active inhibitorssuch as, for, example, 4-a'mino cyclohexene-i, 3-N,N-dimethylaminocyclohexene-l and the corresponding quaternary ammo- The inhibitors maycontain one' nium base containing one methyl ,more on the nitrogen,5-amino cyclo-octene-l, S-amino-paramenthene-l, 2-amino-para-menthene-8.

Also aromatic amines are useful provided they contain an unsaturatedolefinic or acetylenic bond outside the aromatic ring and provided theyare not capable of azoic coupling; as examples.

of such compounds there may be mentioned N- allyl N ,N dimethyl N phenylammonium hydroxide, N,N-diallyl-para-chloroaniline, N,'N,N- triallyl Npara-tolyl ammonium hydroxide, (which compound, it will be noted,contains 16 carbon atoms and 3 olefinic double bonds), N- propargylN,N-dimethyl-N-phenyl ammonium hydroxide.

Also heterocyclic bases are useful provided they contain double bonds ofolefinic character either in the ring or outside the ring, r providedthey contain outside the ring acetylenic triple bonds and also providedthey do not couple. As exam-' ples of such compounds there may bementioned N,N-diallyl furfurylamine, N,N-diallyl-6amino-1,4-benzodioxane, tropidine, N-allyl pyridinium hydroxide.

The inhibitors of the present invention may be added either before orafter the diazotization. However, not all of the inhibitors claimed inthis invention can be added before the diazotization because a greatmany or them would react with nitrous acid. Thus all primary andsecondary amines cannot be added before the diazotization. If theinhibitor is to be added before the diazotizatlon we therefore prefer touse aliphatic tertiary or quaternary compounds. aromatic bases known asice color diazo components may be blended with the inhibitor'and suchblends may be subsequently diazotized in the customary manner andincorporated into a printing paste. The obvious equivalent of thisprocedure is to dissolve the inhibitor and the ice color diazo componentseparately before the diazotization is carried out.

When the inhibitor is added after diazotization also a primary orsecondary. amine may be used. Since printing pastes containing diazoniumsalts are acid, no formation of diazo-amino or diazoimino compounds orof analogous condensation products with amidines or guanidines takesplace. Diazonium salts either stable per Se or stabilized in a customarymanner may be blended with the inhibitor. The obvious equivalent is toadd the inhibitor to a separately prepared diazo solution beiore theprinting paste is made up.

It does not make any different what procedure is used, in every case thethinning of the printing gum is greatly delayed.

In this case the whenever a dry blend with either the ice color diazocomponent or with the diazonium salt is to be made. Obviously thesalts'must be Water soluble, .but it'is not necessary that thecorresponding base is water solublesince the free base would beliberated only after the diazonium salt has been printed on the naphtholprepared goods and after the inhibitor had already accomplished its taskof keeping the printing paste stable.

The invention will be further illustrated with the specific exampleswhich describe typical ombodiments of the present invention. The pactsare by weight.

Example 1 2.56 parts of the zinc chloride double salt of the tetrazoniumchloride derived from o-dianisi- 'dine, diluted with partiallydehydrated magnevantage over a. paste not containing the ailyl triethylammonium chloride that the former retains its viscosity better than thelatter, as is shown by the following'figures:

Relative Relative viscosity viscosity ,Printing paste used measurementmeasurement after half an after 4.7 hours hour Printing paste asdescribed above 33.0 17.0 Same but without inhibitor 26. 5 3. 5

In this experiment the relative viscosities are measured by noting thetime for lead shot weighing .071 gram each to fall 130 millimetersthrough the paste.

Example 2 25 parts of a solution of diazotized 5-nitro-2- amino anisole,equivalent to 0.84 part or reai base, are mixed with a solution of 0.256parts of N-allyl-N,N,N-triethyl ammonium chloride in 11.6 parts of waterand the resulting solution is thoroughly mixed with parts Or 2.5% carcbbeen gum. This paste is used for the production of fast red prints oncotton cloth impregnated with the anilide of 2-hydroxy-3-naphthoic acid.The advantage of this paste over one similarly prepared but without theN-allylN,N,N-triethyl ammonium chloride is shown in the following Itable:

Relative Relative viscosity viscosity Prmtmg paste used measurementmeasurement after three after three minutes hours Printing paste asdescribed above. 19. 6 l4. 2 Same, but Without inhibitor 20.0 10.8

make any diiference whether the base is used as such or whether a watersoluble salt is used. It is however, very difiicult to isolatequaternary bases and in most cases they can not be isolated Theserelative viscosity measurements are the times in seconds for copperplated steel shot Weighing 0.107 gram each to fall millimeters.

Instead of the N-allyl-N,N,N-triethyl ammonium chloride, other watersoluble salts such as fthe sulfate, phosphate, nitrate, ethanesulfonate,

Example 3 the diazonium chloride obtained from 2,5-dichloraniline,corresponding to approximately 50% real base, and 0.331 part ofN-beta-methylallyl-N,N,N-trie thyl ammonium chloride of the followingformula:

- cHFc-cHr-m-m Ha (elm); are dissolved in 21 parts of water, and theresulting solution is intimately mixed with '75 parts of 2.5% oarob beangum. The resulting printthe production of fast prints on fibersimpregnated with the usual ice color coupling components in theusuaLmanner. In each case the relative viscosity of the printing pasteso prepared decreased less rapidly than the relative viscosity' ofsimilar printing pastes prepared without the addition of the quaternarysalt used as inhibitor.

In the following table the relative viscosities made and after a certainlength of time, are compared with the relative viscosities of. similargums not containing the inhibitortaken at the same m p te 1s used forthe preparation of fast ne S... g... e t e etr Parts of n o viscosi m gre a ve re ve Nature Punting water to Kind of thickening gumusedthickening reading 88001151 viscosity Mt! v powder dissolve gumafter 2 .tive viscosity measuremeasure minutes measurement ment mentPercent Hours Contains inhibitor... 21 2. 5 56. 5 1 39. 4 ,A Withoutinhibitor- 21 -6 7- 8 I 1 2. 1 A With inh..bitor 21 3.0 39. 8 21 24. 4 AWithout .nhibitor. 21 3. 0 40. 5 v 21 7. 2 A With inh..bitor 23 5.2634.5 3 34.4 B Without .nhibitor.-- z; 5. 26 35. 0 3 28. 0 B Withinhibitor 21 3.5 121.0 4 I 107.0 C Without inhihiton 21 3. 5 12L 0 4 57.0 C

Norr.-Method iA" consists of the measurement of the time in seconds forbeads weighing 0.097 gram to all 130 millimeters through taken on aBrookfield electn'c viscosimeter-speed 60, spindle No. 3.

scarlet prints upon cottonl cloth impregnated with the anilide of2-hydr0xy-3-naphthoic acid and for the preparation of fast orang printsupon cotton cloth impregnated with the ortho.

phenetidide of 2-hydroxy-3-naphthoic acid in the well-known manner. Theprinting paste so prepared retains its relative viscosity, and hence itsutility for printing much-better than a similar paste whichdoes notcontain the N-betamethyl-allyl-N,N,N-triethyl ammonium chloride, as isshown by the followingfigures:

Printing pastes are made by dissolving in water the numberof parts ofthe zinc chloride double salt of the diazonium chloride obtained from ofreal base and 0.331 part of N-betamethyl allyl-N,N,N-tri ethyl ammoniumchloride, and the resulting solutions are mixed with various aqueousprinting gums. These gums can be used for the gum. Method B" consists intiming in seconds the flow of cc. of

Example 5 3.86 parts of a mixture of the zinc chloride-double salt ofthe diazonium chloride obtained from '3-nitro-4-amino anisole andpartially dehydrated 40 bromide). The mixture is then dissolved in 213-nitro-4-amino anisole equivalent to 0.84 part 7 parts of water and theresulting solution is thon- 'ouglily mixed with parts of 2.5% carob beangum. The resulting paste is used for the production of fast color printsupon fibers .im'-

pregnated with ice color couplin components in the usual manner.

In a similar manner a printing paste is made from 1.62 parts of the zincchloride double salt of the diazonium chloride of 2,5-dich'loroaniline,0.288 part of N-vinyl-N,N,N-trimethyl ammonium bromide, 21 parts ofwater, and 75 parts or 2.5% carob bean gum. This paste is used for theproduction of fast color prints in impregnated cloth in the mannerdescribed above.

The advantages which these printing pastes Time after m by I Time aftermixing for re mg of Second re- Base used {or diazo mung first relativeag second relagg'i viscosity tive viscosity reading Monies Hbura withinhl'bitnl'- 2 58. 9 2 12.8 Without inhibitor- 2 55- 2 2 1. 2 withinhibitoruu 8 61. 8 3 ALB Without inhibitor. 8 52. 7 3 2L 3 The relativeviscosi y readings to tall mm. through the gum.

arethetimesinseeondslorspheticelglessbeadsweighing 0.0976 gram the pastefrom a 10 cc. pipette. Method 0" consistsolreadings Example 6 2.54 partsof the mixture of the zinc chloride double salt of the tetrazoniumchloride derived fromp-dianisidine and partially dehydrated magnesiumsulfate, having a strength equivalent to 29.8% real base, are mixed with0.3 part of N-allyl pyridinium sulfate of the following formula:

2 N )so.

2 and the mixture is dissolved in 22.1 parts of water. The'resultingsolution is intimately mixed with '75 parts of 2.5% carolobean gum. Inan entirely analogous manner, a printingpaste is made from the sameingredients except that.

Relattive iziis- Reliative gs cosi y re cos ty re Inhibitor used I mg 16hour mg 4% hours after mixing after mixing N-allyl pyridinium sulfate-29. 9 17. 1 N -allyl pyridinium chloride; 27. 6 13. 3 None 26. 6 3. 5

These viscosity measurements are the times in seconds for lead shotweighing 0.071 gram each to fall 130 millimeters.

Example 7 A mixture is made of 1.62 parts of the zinc chloride doublesalt of the diazonium chloride derived for example, for the productionof fast bright scarlet prints on cloth impregnated with the anilide of2-hydroxy-3-naphthoic acid; for the production' of bright reddish orangeprints on cloth impregnated with the ortho phenetidide of2-hydroxy-3-naphthoic acid; or for the production of bright yeliowprintson cloth impregnated with bis-acetoacetic acid o-tolidide. Thebeneficial effect of the allyl isothiourea hydrochloride on maintaun''n'g the relative viscosity of the printing paste is shown in thefollowing table:

Relettive vs- Relative vscosi y res cosity rea Prmtmg paste used ingafter ing after 2 minutes 4 hours Printing paste as described above. 41.7 33. 8 Same but without allyl isothiourea...- 41. 3 17.9

These relative viscosity measurements are the times in seconds forspecial glass beads weighing 0.0975 gram each to fall 130 mm.

Example 8 Solutions are made by dissolving in 21 parts of water anamount of the zinc chloride double salt of the diazonium chloridederived from 3-nitro-4- amino anisole equivalent to 08d part of realbase and 0.264 part of allyl isothioureahydrochloride of the followingformula: v

Each solution is mixed with 75 parts of an aqueous gum thickener ofvegetable origin. These printing pastes are suitable for the preparationof fast color prints on fiber impregnated with ice color couplingcomponents in the usual manner.

They are distinguished for their ability to retain their relativeviscosity, and hence their utility for printing a longer tme than simlarpastes prepared without the presence of the allylisothioureahydrochloride. This is shown in the following table:

' Time of Time of first second Method of Water to i First SecondStrength relative visrelative relative Netuix-Jeog'g'r nt g 3531K;Thickening gum used o1!)e gium itn ctgityaifgead- 3:38. viscgsity 2 xdvigcosity cen g rea mg 9 .rnnnapowder mixing reading an?! to ading tion mixing Manta Hours with inhibitor 21 Carob been 2. 5 2 74. 9 1 51. 4A Without inhibitor 21 .-do 2. 6 2 57. 8 1 2. 1 A W ith inhibitor 21Methyl cellulose (Methocel 4000).. 3 2 40. 7 4 30. 8 A Withoutinhibitor- 21 .d0 3 2 40. 6 4 20. 4 A With inhibitor 23 Sweet potatostarch 5. 26 2' 34. 2 3 34.1 B Without inhibitor. 23 do 5. 26 2 35. 0 328. 0 B with inhibitor 21 3. 5 3 117 4 98 C1 Without inhibitor 21 0 3. 53 121 4 57 Cl 1 l or.. gum in xe s are 68 -2 W'th inhib't 21 R P G i d th 8 4 750 4 730 C Without inhibitor 21 .do 8 4 600 4 335 C2N0'rE.Relative viscosity measurements are taken as follows: .A-Time inB-Time in seconds for 10 cc. or paste to flow mm a 10 cc. pipette.C1Releti Reading in centipoises taken on Brooktleld viscosimeter.

seconds for glass beads weighing .0975 gram to fall mm. vs readmg, takenon Brookfleld electric viscosimeter. C2

Example 9 An intimate mixture is made of 10 parts of 3- nitro-4-aminoanisole, 2.5 parts of allyl isothicurea hydrochloride, and'7.5 parts ofcommon salt. This mixture is useful for the preparation of fast printson fibers impregnated with ice color coupling components, as is shown inthe following example:

1.68 parts of the mixture described above is stirred in a. mixture of 5parts of 5N hydrochloric acid, 10 parts of ice water, and to the mixturelowing solution. After 'diazotization is complete, the

acidity to Congo red paper is destroyed by the addition of small amountof sodium acetate solution. The resulting diazo solution is intimatelymixed with 75 parts of 2% aqueous carob bean gum. The resulting viscouspmte is printed upon cloth impregnated with the anilide oi' Z-hydroxy-'3-naphthoic acid in the customary manner.

BrightBordeaux prints are obtained. 'After four hours, such a printinggum is still sufficiently viscous for proper printing, whereas asimilar.

pastemade from a base not mixed with the inusual ice color couplingcomponents, and as in,

Ezamplell In a manner similar to that described in Ex ample 8'printingpastes are made from thezinc v chloride double salt of the diazoniumchlorideof 3-nitro-4-amino anisole "and various gum 'thickeners, butwith 0.288 part of beta-methylallyl f isothioureahydrochloridesuhstituted for the allyl isothiourea used in'Example 8.,Thefresulting printing gums are used for preparationjof. fastcolorprints upon the .fiber prepared with the the example shown above,theseprinting pastes maintain their relative viscosity better thansiinilar printing pastes which do not contain the inhibitor has becomewatery and unsuitable for hibitor. Thisis shown by the following table:

Time af- Parts of Time after ml] 8 Method oi Nature of P inting g ggi ig Thickening gum used lit gi mafi reiiiits gf s cond r e i iirg s m apowder printing t in per viscosity viscosity relative viscosity 23powder cent reading reading reading went I Minutes Hours v i Withinhibitor 01 bean 5.? L2 i 48. 0 A 0 2. i A Methyl cellulose (Methocel4000).. g 2 With inhibitor 23 5. 2e 2 3314 3 3413 B Without inhibitor 235. 26 2 35.0 3 28. 0 3 With inhibitor 21 3. 5 3 120 4 102 C1 Withoutinhibitor 21 0 3. 5 I 3 121 4 57 01 With inhibitor. 21 R. P. G. gum mxed starches 8 4 745 4 735 02 Without inhibitor 21 0 8 4 600 t 4 335 C2Norm-Explanation of viscosity measurements: A-Time in seconds for glassbeads weighing 0.097 gram to fall 1330 mm. B-lime for 10 cc. of paste toflow from a 10 cc. pipette. Brookfleld viscosimeter.

printing. This change in relative viscosity of the gum is shown by thefollowing figures:

m neis tiv s- Relativeflzis- Print gum use cosi r cosi a r g 2 lion. 4him Printing paste as described above.-." 43. 2 21,1 Same but withoutinhibitor 32. 8 2. 9

These relative viscosity measurements are the times in seconds taken forglass beads weighing 0.097 gram to fall 130 millimeters.

- Example 10 A printing gum is made as described in Exam Dle (except forthe fact that 0288- parts of betamethyl allyl isothi'ourea hydrochlorideof thefolformula (obtainabl from thiourea and beta-methylallylchloride)is used in place of 0.264 part of allyl isothiourea preserving itsrelative viscosity for a longer period than similar. paste notcontaining the in- 1 hibitor. This is shown in the following table:

I These relative measurements are the times in seconds for glass beadsweighing 0.097

gram each to tall 130 mm.

(ll-Relative readings taken on Brookfleld-viscosimter. C2-Reading incentipoises taken on 0 Example 12 the-same manner as that described inExample 9 above. The printing paste thus prepared is useful for thepreparation of fast color prints on the fiber which has been impregnatedwith ice color coupling components; for example, when this-paste isprinted upon cotton cloth impregmated with the anilide of2-hydroxy-3-naphthoic acid, bright bluish red prints of very goodfastness properties are produced. The ability of such a paste tomaintain its relative viscosity, and

hence its utilityfor printing is shown in the foilowing table:

' Relattive vtils- Relggiveegvascosiyrea cosiyr Prmtmg paste ing altermg after I 2 min. 4 hours Paste containinginhibitor so. 2 29.1 Same butwithout inhibitor 38. 2 0. 1

These relative viscosity readings indicate the time in seconds forglass-beads weighing 0.097 am to fall 130 millimeters.

Example 13 5.48 parts of a mixture ofthe zinc chloride double salt ofthe diazonium chloride derived from 3- nitro--aminoanisole and partiallydehydrated aluminum sulfate, corresponding to 15.35% real whichi'ssuitable for the production of fast Bor-' ing paste maintain itsrelative viscosity, and

hence its utility for printing, much better than a similar printingpaste which does not contain the allylamine hydrochloride. Thisadvantage is shown in. the following table:

Reiattive vs- Relative vcilscosi y rea cosity rea Printing paste used mg2 min mg 2 hours after mixing aiter mixing Containing allylaminehydrochloride 38. 5 14. 6

Without allylamine hydrochloride 40. l l. 4'

The relative viscosity readings are the times in seconds for copperplated steel shot "weighing 0.107 gram each to fall 130 millimeters.

Example 14 1.575 parts of the zinc chloride double salt of the diazoniumchloride derived from 3-nitro-4- amino anisole is dissolved in 21.5parts of water containing 0.23 part of diallylainine hydrochloride. with'75 parts of 2.5% carob bean gum. The resulting printing paste is suitedfor the production of fast Bordeaux prints upon cotton cloth impregnatedwith the anilide of 2-hydroxy-3-naphthoic acid. The printing paste soprepared retains its relative viscosity, and hence its utility Theresulting solution is intimately mixed for printing, much better than asimilar paste prepared in exactly the same manner but without thediallylamine hydrochloride. This advantage is shown in the followingtable:

Relative vs- Relattive vtiiscosity rea oosi yrea Printing paste used mgafter inggiter 2 min. 2 ours Containing diallylamine hydrochlor' e 53. 620. 0 Without diallylamine hydrochloridc 45. 6 1. 3

These relative viscosity readings are the times in seconds for copperplated steel shot'weighing approximately 0.10'1 gram each to fall 1-30millimeters. Example 15 1.5? parts of the zinc chloride double salt -ofthe diazonium chloride of 3-nitro-4-amino anisole, and 0.446 part oftetra-allyl ammonium bromide are dissolved in 21 parts of-water and theresulting solution is intimately .mixed with '75 aseaeee deaux prints oncloth impregnated with the ani- .lide of 2-hydroxy-3-naphthoic acid.This print- 7 ltelatiitre l'telatige Diazotized amine in Thinninginhibitor in 500$ y SW51 y printing paste printing paste gfgi E -12 min.hours 3-nitro-4-amino ani- Tetra-allyl ammoni- 69. 5 48. 2

sole. um bromide.

Iio None 62.4 1.3 2, 5-d1chlor aniline... Tetra-allyl emrnoniv96. 8 90.3

um bromide. Do None 83.3 19.0

These relative viscosity measurements are the times in seconds forcopper plated steel shot weighing approximately 0,107 gram each to fall130 millimeters.

Example 16' 1.575 parts of the zinc chloride double salt of thediazonium chloride derived from 3-n'itro-4- amino anisole and 0.34 partN-allyl-N,N-dimethyl-N-phenyl ammonium chloride are dissolved inRelative yis- R 1 cosity reading a we Printing paste used after H) 2 to4 cgfstlgyzriidlnsg .rmn.

Containing thinning inhibitor 44. 6 25. 4 Without thinning inhibitor:45. 0 1.0

These relative viscosity readings are the times in seconds for copperplated steel shot weighing approximately 0.107 gram each to fall 130millimeters. 1

Example 17 5.4:; parts of a. mixture of'the" z'ii'i chloride double saltof the diazonium chloride vderived from 3-nitro-4-amino anisole andpartially dehydrated aluminum sulfate, corresponding to a strength of15.35% real base, are-dissolved in 21 parts of water along with 0.20partof N-allyl urea. The resulting solution is intimately mixed with 75parts of 2.5% carob bean gum. The resulting printing paste is valuablefor the preparation of fast Bordeaux prints upon cotton cloth parts of2.5% carob bean gum. The resulting printing paste is used for theproduction of test Bordeaux prints upon cotton cloth impregnated witharylides of 2-hydroxy-3-naphthoic acid.

In a similar manner, 1.63 parts-of the zinc chloride double salt of thediazonium chloride of 2,5- dichloraniline is mixed'with 0.46 parts oftetra allyl ammonium bromide and the resulting mixture is dissolved in21 parts of water. This solution is then intimately mixed ,with 75 partsof 2.5% carob bean gum to form a printing paste which is eminentlysuited for the production of bright scarlet prints upon clothimpregnated with the anilide of 2-hydroxy-3-h'aphthoic acid.

The advantages that these printing pastes possess over similarlyprepared pastes not containing tetra allyl ammonium bromide, are shownin the following table:

impregnated with arylides of 2-hydroxy-3-naphthoic acid, and is superiorto a. similar paste which does not contain the allyl urea because of thefact that it retains its relative viscosity and, hence, its utility forprinting much better. This advantage is shown in the following table:

Relative vis- Relative vis- Prmtingpaste used cosity reading cosityreading after 2 min. after 2 hours Containin allyl urea. 39. 8 1B. 6Without lyl urea 40. 1 1. 4

These relative. viscosity measurements are the times in seconds forcopper plated steel shot weighing approximately @107 gram each to fallmillimeters.

manner: v An amount of the zinc chloride double salt of ous mineralacids and containing at least one oleflnic double bond for 12 carbonatoms, organic nitrogenous bases soluble in aqueous mineral acidscontaining at least one acetylenic triple also free from primary andsecondary aminogroups it used together with amines before.diazotization, the amount of the nitrogenous base of a carbohydratethickener.

2. A printing paste containing a carbohydrate thickener, at least onewater soluble diazonium salt derived from an ice color diazo componentand an organic compound having not more than 16 carbon atoms belongingto the group consistbeing sufiicient to substantially inhibit thinning 77 g g i gg g fg ggg 'gzfi fiz 23 3x 22: bond for 12 carbon atoms, andwater soluble salts arts is mixed with 0 512 parts of 'anyl guanidme ofthe above bases, this compound being free from p constituents capable ofazoic coupling, of consulfate and the mixture is dissolved. in enoughdensation with the diazomum salt to form dlazowater to make 25 parts'ofsolution. The resultmg Solution is mtimatel mixed with 75 parts ammo ordiazoimino compounds under acid conditions, or catalyticall'ydecomposing the discoof Carob bean These Punting pastes nium salt atroom temperature the amount of the i are used for the preparation offast color prints .r e

ogenous base present being suflicient to subupcn mpregnated the amide2415" stantially inhibit thinning of the carbohydrate droxy-a-naphthoicacid. These printing pastes tmckener retain their relative viscosity andhence their util- 1 ity to the printer, very much better than similarcomposltmn j j w 9 01mm 1 whtch pastes Similarly prepared but withoutthe any] the diazonium salt 15 a diazoniumchloride-zinc guanidinesulfate. Thisadvantage may be seen chloride double Saltby consulting thefollowing table: 4. A composition according to claim 2 inwhicli Relativevis- Relativevis- Color of print on Base used for zinc chlorideThinniug'inhibitor in cosity meascoslty measanilide of 2-hydouble saltprinting paste urement urement droxy-3-nsphthoic after2min aiterihrs.acid 2,5-dichloraniline.. Allyl guanidine sulfate. 66.8 66.0 Yellowishscarlet.

' DQ v None 61.2 10.2 Do. 4-nitro-2-amino anisolo- Allyl guanidinesulfate... 69. 4 65. 6 Reddish scarlet. Do None 76.2 18.2 Do.3-nitro4-amino aniso Allylguanidine sulfate. 85.6 40.0 Bordeaux.

None 83.2 0.4 o.

Allyl guanidine suliate-. 66.4 49.6 New blue. None 71. 4 9. 2 Do.

These relative viscosity measurements are the the diazonium salt is adiazonium chloride zinc times in seconds for copper plated steel shotchloride double salt. I v weighing 0.107 gram each to fall 130millimeters. 5. A composition according to claim 1 in which Thisapplication is in part a continuation oifour 40 the nitrogenous base isan allylguanidine. co-pending application, serial No. 437,201, filed 6.A-composition according to claim 2 in which April 1, 1942. thenitrogenous base is an allylguanidine.

We claim: p 7. A composition according to claim 1 in which 1. Acomposition suitable for the preparation the nitrogenous compound is atetra-allylammoof printing pastes containing carbohydrate gum niumcompound. thickeners comprising an ice color forming com- 8. Acomposition according to claim 2 in which ponent included in the groupconsisting of comthe nitrogenous compound is a tetra-allylammopositionscontaining water soluble diazonium salts nium compound. 1 r andintermediates therefor consisting of amines 9. A'composition comprisingwater soluble didiazotizable to produce compositions containing 59azonium salts derived from an ice color diazo I water soluble diazoniumsalts, the color forming component and an organic compound with notcomponent having admixed therewith'an organic more than 16 carbon atomsselected from me compound with not more than sixteen carbon groupconsisting of organic nitrogenous bases sol-' atoms selected from thegroup of organic nitroguble in aqueous mineral acids and containing atenous bases soluble in aqueous mineral acids least one olefinic doublebond for 12 carbon and containing at least one oiefinic double bondatoms, organic nitrogenous bases soluble in aquefor twelve carbon atoms,organic nitrogenous ous mineral acids containing at least one acetbasessol bl in q eousmineral acids containing ylenic triple bond for twelvecarbon atoms, and at least o a ty t pl b nd for tw lve water solublesalts oi the above bases, this combon atoms, and water soluble saltsoi!the above 60 poundbemg f 1mm constituents capable f bases, this compoundbeing free from constitazoic coupling, f forming dim amino or diam uentscapable of aizoic coupling, of torminigddiazo unmo c'ompounds under acidconditions and of amino or diazo im no compounds under ac conditions, ofcatalytically'decomposing diazonium gggg gg' gf g ggg 2 :5 gz g z g z igi az salts at room temperature, this compound being pe I g base beingsumcient to substantially inhibit thinning of a carbohydrate thickener.

'10. A composition according to claim 1 in the nitrogenous compound isan allyl urea.

FREDERIO H. ADAMS; HANS z. :LECHER. WILLIAM B. HARDY.

ing of organic nitrogenous bases soluble in aque-'

